Method for producing new polynuclear poly(formylphenol)

ABSTRACT

Produce the target substance, or a polynuclear poly(formylphenol) expressed by General Formula (2), in an industrial setting with ease and at high purity by causing a polynuclear poly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol) to react with hexamethylene tetramine in the presence of an acid and then hydrolyzing the obtained reaction product.

This application is the U.S. National Phase under 35 U.S.C. §371 ofInternational Application PCT/JP2007/061107, filed May 31, 2007, whichclaims priority to Japanese Patent Application No. 2006-151973, filedMay 31, 2006, and No. 2006-161694, filed Jun. 9, 2006. The InternationalApplication was published under PCT Article 21(2) in a language otherthan English.

TECHNICAL FIELD

The present invention relates to a method for producing a polynuclearpoly(formylphenol) in an industrial setting with ease and at highpurity. To be specific, the present invention relates to a method forproducing a polynuclear poly(formylphenol) in an industrial setting withease and at high yield and high purity by using as the material apolynuclear poly(hydroxymethylphenol) or polynuclearpoly(alkoxymethylphenol) that can be obtained easily from a polynuclearpolyphenol, and causing the material to react with hexamethylenetetramine in the presence of an acid and then hydrolyzing the obtainedreaction product.

PRIOR ART

Traditionally, the Reimer-Tiemann reaction that uses chloroform andaqueous sodium hydroxide solution, as well as the Duff reaction thatuses hexamethylene tetramine and an acid catalyst such astrifluoroacetate, are known as ways to introduce a formyl group to aphenol. These methods are both based on a reaction to directly introducea formyl group to a phenyl nucleus by means of substitution, where theformer method uses a large amount of halogenated hydrocarbon andprovides a low yield, while the latter method, based on an examinationby the inventors for the present invention, in many cases is unable tosynthesize the target substance at a high yield even when applied to apolynuclear phenol as shown in a comparative example included in thepresent application for patent, or requires a very long reaction time.

Also, a method to cause a given amount of phenol to react with the sameamount of alkyl magnesium bromide and then cause the obtained reactionproduct to react with formaldehyde to achieve formylation is describedin J. Chem. Soc., Perkin Trans. (1978, 318 to 321). However, this methodhas a drawback of requiring a large amount of expensive alkyl magnesiumbromide.

A method to cause a phenol to react with tin tetrachloride and thencause the obtained reaction product to react with formaldehyde toachieve formylation is described in J. Chem. Soc., Perkin Trans. (1978,1862 to 1865). However, this method uses a large amount of expensive tintetrachloride and also requires treatment of a large amount ofwastewater generated from the reaction, which is undesirable. Also inthis literature, a salicylaldehyde is synthesized from tin tetrachlorideby also using 2-hydroxy benzyl alcohol. However, an examination by theinventors for the present application found that this method could notbe applied favorably to a polynuclear polyphenol.

A method to oxidize a hydroxy methyl phenol to produce a hydroxy methylbenzaldehyde is described in Japanese Patent Laid-open No. 52-136141.However, this method is based on a gas/liquid reaction and therefore thereaction yield changes easily according to the agitation condition, etc.Also, pure oxygen is used, which makes it difficult to use this methodin an industrial setting.

On the other hand, among the various methods to synthesize abis(formylphenol) or polynuclear poly(formylphenol), a method to causesalicylaldehyde and formaldehyde to react with each other using an acidcatalyst is described in Chungnam National University IndustrialTechnology Lab Papers Vol. 4, No. 2 (1977). However, the substitutedbenzaldehyde, which is used as the material, is expensive and if thereaction uses a carbonyl compound other than formaldehyde, the lowreactivity causes benzaldehyde itself to polymerize under conditionswhere the carbonyl compound undergoes reaction. These factors make itdifficult to apply this method.

Also, a method to tetraformylate a bisphenol is described inToku-Kai-Hei 5-125032. However, the yield is low and, because a largeamounts of hexamethylene tetramine and acid are used compared to thebisphenol, the volumetric efficiency is poor and therefore this methodcannot be implemented in an industrial setting.

Furthermore, a method to cause 5-iodine-3-tert-butyl salicylaldehyde and1,3,5-triethynyl benzene with each other in the presence ofbis(triphenolphosphine)palladium, iodinated copper and triethyl amine toobtain 1,3,5-tris[(5-tert-butyl-3-formyl-4-hydroxyphenyl)ethynyl]benzeneis described in WO Laid-open No. 2004/050231. However, this method usesexpensive materials.

As explained above, it was difficult under any conventional method toproduce a polynuclear formyl phenol in an industrial setting with easeand at high yield and high purity.

Patent Literature 1: Japanese Patent Laid-open No. Sho 52-136141 PatentLiterature 2: Japanese Patent Laid-open No. Hei 5-125032 PatentLiterature 3: WO Laid-open No. 2004/050231 Non-patent Literature 1: J.Chem. Soc., Perkin Trans. (1978, 318 to 321, 1862 to 1865) Non-patentLiterature 2: Chungnam National University Industrial Technology LabPapers Vol. 4, No. 2 (1977)

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

The present invention relates to a method for producing a polynuclearformyl phenol in an industrial setting with ease and at high yield andhigh purity. To be specific, the present invention relates to a methodfor producing a polynuclear formyl phenol by using as the material apolynuclear poly(hydroxymethylphenol) or polynuclearpoly(alkoxymethylphenol) that can be obtained easily from a polynuclearpolyphenol.

Means for Solving the Problems

After examining diligently to achieve the aforementioned purpose, theinventors found that the desired polynuclear formyl phenol could beobtained at high yield as a bis(formylphenol) or a polynuclearpoly(formylphenol) having three or more hydroxy-substituted phenolnuclei, by using as the direct material a hydroxymethyl-substituted oralkoxymethyl-substituted bisphenol or polynuclearpoly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol) thatcan be obtained easily by, for example, methylolation of a polynuclearpolyphenol being a subject of the present invention, such as a bisphenolor a polynuclear polyphenol having three or more hydroxy-substitutedphenol nuclei, and then causing the material to react with hexamethylenetetramine in the presence of an acid, followed by hydrolyzation of theobtained reaction product to convert into a formyl group the hydroxymethyl group or alkoxy methyl group substituted to the phenyl nucleus.Based on the above findings, the inventors completed the presentinvention.

To be specific, the present invention provides a method for producing apolynuclear poly(formylphenol) expressed by General Formula (2), whereinsaid method is characterized in that a polynuclear polyphenol expressedby General Formula (1) is caused to react with hexamethylene tetraminein the presence of an acid and then the reaction product is hydrolyzed.

(In the formula, all Rs may be the same or different and respectivelyrepresent a hydrogen atom or an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have an ether group. R₁, R₂ and R₃ may be thesame or different and respectively represent a hydrocarbon group,hydrocarbon group containing oxygen atom, hydroxyl group, halogen groupor halogenated hydrocarbon group; a and c respectively indicate aninteger of 0 or 1 to 3, while b indicates an integer of 0, 1 or 2; l andn respectively indicate an integer of 1 to 3; m indicates an integer of0, 1 or 2; X indicates a bond group or single bond; and Y indicates abivalent alkylene group.)

(In the formula, R₁, R₂, R₃, a, b, c, l, m, n, X, and Y indicate thesame things represented by the corresponding symbols in General Formula(1).)

With a polynuclear polyphenol expressed by the aforementioned GeneralFormula (1), if m is 0, X is a bivalent bond group or a single bond, andl+n is 2 in the formula, then a method for producing a polynuclearpoly(formylphenol), wherein the polynuclear polyphenol is a bisphenolexpressed by General Formula (3) specified below, and wherein similarlythe polynuclear poly(formylphenol) expressed by the aforementionedGeneral Formula (2) is a bis(formylphenol) expressed by General Formula(4) specified below, is a favorable embodiment of the present invention.

(In the formula, all Rs may be the same or different and respectivelyrepresent a hydrogen atom or an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have an ether group, where n indicates aninteger of 0 or 1 to 3. Both R₁s may be the same or different andrespectively represent a hydrocarbon group, hydrocarbon group containingoxygen atom, halogenated hydrocarbon group, hydroxyl group or halogengroup. X indicates a bivalent bond group or a single bond.)

(In the formula, R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3).)

Also, a method for producing a polynuclear poly(formylphenol), whereinsaid method is characterized in that a bis(hydroxymethylphenol)expressed by General Formula (6), being a bisphenol expressed by theaforementioned General Formula (3) where R is a hydrogen atom, isobtained by causing a bisphenol expressed by General Formula (5) toreact with formaldehyde in the presence of an alkali catalyst, is afavorable embodiment of the present invention.

(In the formula, R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3), and at least one of theo-position and p-position of the hydroxyl group is not substituted.)

(In the formula, R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3), and the substitutionposition of the hydroxymethyl group corresponds to the o-position orp-position relative to the hydroxyl group.)

A method for producing a polynuclear poly(formylphenol) according to anembodiment of the present invention, wherein said method ischaracterized in that a bis(alkoxymethylphenol), being a bisphenolexpressed by the aforementioned General Formula (3) where R is analiphatic hydrocarbon group that may have an aromatic hydrocarbon group,hydroxyl group or aliphatic hydrocarbon group that may have an ethergroup, is obtained by causing a bisphenol expressed by theaforementioned General Formula (5) to react with formaldehyde in thepresence of an alkali catalyst and then causing the obtainedbis(hydroxymethylphenol) expressed by the aforementioned General Formula(6) to further react with an alcohol expressed by General Formula (7)specified below in the presence of an acid catalyst, is a favorableembodiment of the present invention.

[Chemical 7]R—OH  General Formula (7)(In the formula, R represents an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group or aliphatichydrocarbon group that may have an ether group.)

Also, a method for producing a polynuclear poly(formylphenol), whereinwith respect to a polynuclear polyphenol expressed by the aforementionedGeneral Formula (1), the polynuclear polyphenol where m in the formulais an integer of 0, 1 or 2, but where if m is 0, then X is a trivalentto hexavalent bond group with l+n being 3 to 6, is a polynuclearpolyphenol expressed by General Formula (8) specified below, and whereinsimilarly the polynuclear poly(formylphenol) expressed by theaforementioned General Formula (2) is a polynuclear poly(formylphenol)expressed by General Formula (9) specified below, is another favorableembodiment of the present invention.

(In the formula, all Rs may be the same or different and respectivelyrepresent a hydrogen atom or an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have anether group. R₁, R₂ and R₃ may be thesame or different and respectively represent a hydrocarbon group,hydrocarbon group containing oxygen atom, hydroxyl group, halogen groupor halogenated hydrocarbon group; a and c respectively indicate aninteger of 0 or 1 to 3, while b indicates an integer of 0, 1 or 2; l andn respectively indicate an integer of 1 to 3; m indicates an integer of0, 1 or 2; X indicates a bond group or a single bond; and Y indicates abivalent alkylene group. If m is 0, however, X is a trivalent tohexavalent bond group and l+n is 3 to 6.)

(In the formula, R₁, R₂, R₃, a, b, c, l, m, n, X and Y indicate the samethings represented by the corresponding symbols in General Formula (8).)

Also, a method for producing a polynuclear poly(formylphenol)accordingto an embodiment of the present invention, wherein said method ischaracterized in that a polynuclear poly(hydroxymethylphenol) expressedby General Formula (11) specified below, being a polynuclear polyphenolexpressed by the aforementioned General Formula (8) where R is ahydrogen atom, is obtained by causing a polynuclear polyphenol expressedby General Formula (10) specified below to react with formaldehyde inthe presence of an alkali catalyst, is a favorable embodiment of thepresent invention.

(In the formula, R₁, R₂, R₃, a, b, c, l, m, n, X and Y indicate the samethings represented by the corresponding symbols in General Formula (1),and at least one of the o-position and p-position of the hydroxyl groupis not substituted. If m is 0, however, X is a trivalent to hexavalentbond group and l+n is 3 to 6.)

(In the formula, R₁, R₂, R₃, a, b, c, l, m, n, X, and Y indicate thesame things represented by the corresponding symbols in General Formula(1), and the substitution position of the hydroxy methyl groupcorresponds to the o-position or p-position relative to the hydroxylgroup. If m is 0, however, X is a trivalent to hexavalent bond group andl+n is 3 to 6.)

Also, a method for producing a polynuclear poly(formylphenol)accordingto an embodiment of the present invention, wherein said method ischaracterized in that a polynuclear poly(alkoxymethylphenol), being apolynuclear polyphenol expressed by the aforementioned General Formula(8) where R is an aliphatic hydrocarbon group that may have an aromatichydrocarbon group, hydroxyl group or aliphatic hydrocarbon group thatmay have an ether group, is obtained by causing a polynuclear polyphenolexpressed by the aforementioned General Formula (10) to react withformaldehyde in the presence of an alkali catalyst and then causing theobtained polynuclear poly(hydroxymethylphenol) expressed by theaforementioned General Formula (11) to further react with an alcoholexpressed by General Formula (12) specified below in the presence of anacid catalyst, is a favorable embodiment of the present invention.

[Chemical 12]R—OH  General Formula (12)(In the formula, R represents an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group or aliphatichydrocarbon group that may have an ether group.)

Under a production method conforming to the present invention, thetarget compound, or polynuclear poly(formylphenol), is expressed by theaforementioned General Formula (2), where R₁, R₂ and R₃ may be the sameor different and respectively represent a hydrocarbon group, hydrocarbongroup containing oxygen atom, hydroxyl group, halogen group orhalogenated hydrocarbon group, but preferably a hydrocarbon group. Bondgroup X is a single bond or bivalent to hexavalent bond group, such as ahydrocarbon group, oxygen atom-containing group, sulfur atom-containinggroup, nitrogen atom-containing group or halogen atom-containing group,but preferably a hydrocarbon group. Bond group Y is a bivalent alkylenegroup.

Also, a and c (indicated by n in General Formulas (3) to (6))respectively indicate an integer of 0 or 1 to 3; b indicates an integerof 0, 1 or 2; l and n respectively indicate an integer of 1 to 3; and mindicates an integer of 0, 1 or 2. Here, if m is 0 and X is a bivalentbond group or a single bond and l+n is 2, then the polynuclearpoly(formylphenol) is a bis(formylphenol). If m is not 0, or X is atrivalent to hexavalent bond group and l+n is 3 to 6, then thepolynuclear poly(formylphenol) is a polynuclear poly(formylphenol)having three or more hydroxy-substituted phenol nuclei in its skeletalstructure.

Accordingly, under a production method conforming to the presentinvention, the target compound, or polynuclear poly(formylphenol)expressed by the aforementioned General Formula (2), is represented by abis(formylphenol) expressed by the aforementioned General Formula (4)if, in the formula, m is 0, X is a bivalent bond group or a single bondand l+n is 2. Here, in the aforementioned General Formula (4), X is abivalent bond group or a single bond, where the bivalent bond group,although not specifically limited as long as it is a bis(formylphenol)having a bond group to which a production method under the presentinvention can be applied, may be a hydrocarbon group, oxygenatom-containing group, sulfur atom-containing group, nitrogenatom-containing group or halogen atom-containing group, among others.Examples of the hydrocarbon group include a saturated or unsaturatedhydrocarbon group, polycyclic or monocyclic alicyclic hydrocarbon group,aromatic hydrocarbon group or heterocyclic hydrocarbon group, ofstraight or branched chain that may have a substitution group.

As for the aforementioned bivalent hydrocarbon group, specific examplesinclude, among others: bivalent noncyclic saturated hydrocarbon groupswith a carbon atom number of 1 to 30, or preferably 1 to 15, such asmethylene, ethylene, propylene, 2,2-propylidene, 1,1-propylidene,2,2-butylidene, hexamethylene, n-dodecylene and other alkylene groupsand alkylidene groups; bivalent noncyclic unsaturated hydrocarbon groupssuch as vinylene, 1,2-ethinediyl, propenylene, 2,4-hexadiene-1,6-ylene,2-butenylene and 2-methylene-1,3-propandiyl; bivalent monocyclicalicyclic hydrocarbon groups with a carbon atom number of 3 to 15, orpreferably 5 to 10, such as cyclopentylidene, cyclohexylidene,1,4-cyclohexylene, 1,2-cyclohexenylene and 2,4-cyclohexadiene-1-ylidene;bivalent monocyclic aromatic hydrocarbon groups such as P-phenylene,2-propyl-1,4-phenylene and other phenylene groups; bivalent condensedpolycyclic hydrocarbon groups such as 2,3-indenylidene, 1,2-naphthylene,2,7-phenanthrene and 9,9-fluorenylidene; bivalent crosslinked cyclichydrocarbon groups such as bicyclo[2.2.1]heptane-2,3-diyl, 6-ethylbicyclo[2.2.1]heptane-2,3-diyl,tetracyclo[4.4.0.1^(2,5)0.1^(7,10)]dodecene-3,4-diyl andadamantane-1,3-diyl; bivalent spiro hydrocarbon groups such asspiro[3.4]octane-7,8-diyl; bivalent polycyclic aggregated hydrocarbongroups such as 1,1′-biphenyl-4,4′-diyl, p-terphenyl-4,4″-diyl,1,1′-diphenyl methane-4,4′-diyl and stilbene-4,4′-diyl; and terpenehydrocarbon groups such as 2-pinene-10-ylidene and5-norbornene-2,3-diyl.

Substitution groups that can be contained in the aforementioned bivalenthydrocarbon groups include bivalent substitution groups or monovalentsubstitution groups that can act as a bond group, where specificexamples include, among others, the aforementioned bivalent hydrocarbongroups or monovalent hydrocarbon groups corresponding to theaforementioned bivalent hydrocarbon groups, such as monovalent noncyclicsaturated hydrocarbon groups, noncyclic unsaturated hydrocarbon groups,monocyclic alicyclic hydrocarbon groups, monocyclic aromatic hydrocarbongroups, condensed polycyclic hydrocarbon groups, crosslinked cyclichydrocarbon groups, polycyclic aggregated hydrocarbon groups, spirohydrocarbon groups and terpene hydrocarbon groups. To be specific,examples include, among others: monovalent noncyclic saturatedhydrocarbon groups with a carbon atom number of 1 to 30, or preferably 1to 15, such as methyl, ethyl, isopropyl, tert-butyl, sec-butyl,isobutyl, t-octyl, n-dodecyl and other alkyl groups; monovalentnoncyclic unsaturated hydrocarbon groups such as vinyl, aryl,hexa-2,4-diene-1-yl and butane-2-en-1-yl; monovalent monocyclicalicyclic hydrocarbon groups with a carbon atom number of 3 to 15, orpreferably 5 to 10, such as cyclopentyl, cyclohexyl, cyclohexene-1-yland cyclohexa-2,5-diene-1-yl; monovalent monocyclic aromatic hydrocarbongroups such as phenyl, 2-propyl-phenyl and other phenyl groups;monovalent condensed polycyclic hydrocarbon groups such as indene-2-yl,1-naphthyl, phenanthrene-2-yl and fluorene-9-yl; monovalent crosslinkedcyclic hydrocarbon groups such as bicyclo[2.2.1]heptane-2-yl, 6-ethylbicyclo[2.2.1]heptane-2-yl,tetracyclo[4.4.0.1^(2.5)0.1^(7,10)]dodecene-3-yl and adamantane-2-yl;monovalent spiro hydrocarbon groups such as spiro[3.4]octane-7-yl;monovalent polycyclic aggregated hydrocarbon groups such as1,1′-biphenyl-4-yl, P-terphenyl-4-yl, 1,1′-diphenyl methane-4-yl andstilbene-4-yl; and terpene hydrocarbon groups such as 2-pinene-10-yl and5-norbornene-2-yl.

Hydrocarbon groups containing the aforementioned substitution groupsinclude, among others, methyl ethyl methylene, methyl isobutylmethylene, cyclohexyl methyl methylene, dicyclohexyl methylene, diphenylmethylene, phenyl methylene and biphenyl methylene. Also, examples ofsubstitution groups containing at least one of an oxygen atom, nitrogenatom, sulfur atom and halogen atom, etc., include: substitution groupscontaining monovalent methoxy, ethoxy, cyclohexyloxy or other alkoxygroup, phenoxy or other aryloxy group, 4-methoxy phenyl group, 2-methoxyphenyl group, furyl group or other ether group; substitution groupscontaining a carbonyl group such as an acetyl, propionyl, butyrylbenzoyl or other acyl group; substitution groups containing a primary,secondary or tertiary ester group such as an acryloyloxy,methacryloyloxy, acetoxy, t-butoxy, benzoyloxy or other acyloxy group;substitution groups containing an hydroxyl group such as a hydroxylgroup or 4-hydroxy phenyl, 4-hydroxy phenol methyl, 3-hydroxy-n-butyl or2-hydroxy ethyloxy; and fluorine atoms and other halogen atoms,halogenated hydrocarbon groups, monovalent amino groups, bivalent ethergroups, carbonyl groups, ester groups, amid groups, imino groups,sulfide groups, and the like.

Accordingly, specific examples of bivalent hydrocarbon groups containinga substitution group including at least one of an oxygen atom, nitrogenatom, sulfur atom and halogen atom include, among others:di(trifluoromethyl)methylene group, 4-hydroxy-3-methoxy phenyl methylenegroup (Chemical Formula 1) and other substituted methylene groups. Otherexamples include a group expressed by Chemical Formula 2 specified belowwhere two methylene groups are provided at both ends of a hydroxyphenylene group, as well as other monovalent heterocyclic groups such asthiophene-2-yl, furan-2-yl, quinoline-2-yl, 2H-pyran-2-yl and1,4-dihydro-4-pyridyl.

Furthermore, specific examples of bivalent bond groups where bond groupX is an oxygen atom-containing group, sulfur atom-containing group,nitrogen atom-containing group or halogen atom-containing group include,among others: bivalent hetero compound groups such as a carbonyl group,ether group, oxocarbonyl group (carboxylate group), sulfide group,sulfoxide group, sulfone group, thioketone group, thiocarbonyl group,carbonyl dioxy group, sulfonyl dioxy group, azo group, hydrazo group,imino group and ureilene group; or bond groups that bond a hydroxyphenyl group in General Formula (3) or (4) specified below via any ofthe foregoing with a hydrocarbon group, such as 1,1′-diphenylether-4,4′dicarbonyl group, 1,1′-diphenyl sulfide-4,4′-dicarbonyl group,terephthaloyl group, 4,4′-methylene dioxy diphenyl group,2,6-naphthylene dioxy group, methylene dioxy group, malonyl group,succinyl group, fumaloyl group and maloyl group. Favorable choices asthe overall bond group X include saturated hydrocarbon groups,hydrocarbon groups containing an unsaturated bond including onlyaromatic hydrocarbon groups, saturated hydrocarbon groups containing aprimary or secondary ester group, and saturated hydrocarbon groupscontaining an ether group (excluding 1,2-epoxide, 1,3-epoxide and acetalgroups), among which saturated hydrocarbon groups, and hydrocarbongroups containing an unsaturated bond including only aromatichydrocarbon groups, are particularly desirable.

(In the formula, all Rs may be the same or different and respectivelyrepresent a hydrogen atom or an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have an ether group, where n indicates aninteger of 0 or 1 to 3. Both R₁s may be the same or different andrespectively represent a hydrocarbon group, hydrocarbon group containingoxygen atom, halogenated hydrocarbon group, hydroxyl group or halogengroup. X indicates a bivalent bond group or a single bond.)

(In the formula, R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3).)

Also, with respect to a bis(formylphenol) expressed by General Formula(4), R₁ in the formula represents a hydrocarbon group, hydrocarbon groupcontaining oxygen atom, halogenated hydrocarbon group, hydroxyl group orhalogen group, where n indicates an integer of 0 or 1 to 3, and if n is2 or 3, both R₁s may be the same or different.

As for R₁, if R₁ is a hydrocarbon group, then it is a monovalenthydrocarbon group that can be substituted to the aforementioned bondgroup X, where specific examples of such hydrocarbon group include,among others, a saturated or unsaturated hydrocarbon group, polycyclicor monocyclic alicyclic hydrocarbon group, aromatic hydrocarbon group orheterocyclic hydrocarbon group, of straight or branched chain which mayhave a substitution group.

Specific examples of the aforementioned monovalent hydrocarbon groupinclude, among others: monovalent noncyclic saturated hydrocarbon groupswith a carbon atom number of 1 to 30, or preferably 1 to 15, such asmethyl, ethyl, isopropyl, tert-butyl, sec-butyl, isobutyl, n-hexyl,t-octyl, n-dodecyl and other alkyl groups; monovalent noncyclicunsaturated hydrocarbon groups such as vinyl, aryl, hexa-2,4-diene-1-yland 2-butane-1-yl; monovalent monocyclic alicyclic hydrocarbon groupswith a carbon atom number of 3 to 15, or preferably 5 to 10, such ascyclopentyl, cyclohexyl, 4-n-butyl cyclohexyl, 2-cyclohexe-3-yl andcyclohexa-2,5-diene-1-yl; monovalent monocyclic aromatic hydrocarbongroups such as phenyl and 2-propyl-phenyl; monovalent condensedpolycyclic hydrocarbon groups such as indene-2-yl, 1-naphthyl,phenanthrene-2-yl and fluorene-9-yl; monovalent crosslinked cyclichydrocarbon groups such as bicyclo[2.2.1]heptane-2-yl, 6-ethylbicyclo[2.2.1]heptane-2-yl,tetracyclo[4.4.0.1^(2,5)0.1^(7,10)]dodecene-3-yl and adamantane-2-yl;monovalent spiro hydrocarbon groups such as spiro[3.4]octane-7-yl;monovalent polycyclic aggregated hydrocarbon groups such as1,1′-biphenyl-4-yl, P-terphenyl-4-yl, 1,1′-diphenyl methane-4-yl andstilbene-4-yl; terpene hydrocarbon groups such as 2-pinene-10-yl and5-norbornene-2-yl; and monovalent heterocyclic hydrocarbon groups suchas furan-2-yl and 2H-pyran-2-yl. Substitution groups that can besubstituted to these monovalent hydrocarbon groups are the same as themonovalent hydrocarbon groups that can be substituted to bivalenthydrocarbon groups pertaining to bond group X.

The oxygen atom-containing hydrocarbon group is a hydrocarbon groupwhere one or more oxygen atoms bond in the chemical structure, wherespecific examples include, among others: substitution groups containinga methoxy, ethoxy, cyclohexyloxy or other alkoxy group, phenoxy or otheraryloxy group, 4-methoxy phenyl group, 2-methoxy phenyl group, furylgroup or other ether group; substitution groups containing a carbonylgroup such as an acetyl, propionyl, butyryl benzoyl or other acyl group;substitution groups containing a primary, secondary or tertiary estergroup such as an acryloyloxy, methacryloyloxy, t-butoxy, acetoxy,benzoyloxy or other acyloxy group; and substitution groups containing anhydroxyl group such as 4-hydroxy phenyl, 4-hydroxy phenol methyl,3-hydroxy-n-butyl or 2-hydroxy ethyloxy.

Examples of halogenated hydrocarbon groups include trifluoromethyl and3-bromo-n-propyl.

If R₁ is a halogen group, then specific examples include a chlorineatom, bromine atom and fluorine atom, among others.

Favorable forms of R₁ are those having a carbon atom number of 1 to 20,and oxygen atom number of 0 to 2, where an alkyl group with a carbonatom number of 1 to 10 and cycloalkyl group with a carbon atom number of5 to 10 are particularly desirable. Cases where R₁ is a hydrocarbonhaving a hydroxyl group, ether group or halogen group (bromine,chlorine, etc.,) in the α-position, or specifically a hydroxy methylgroup or alkoxy methyl group having such characteristics, are notdesirable. Take note, however, that if n is 2 or 3, then allsubstitution positions of R₁ may be the same or different.

As for a bis(formylphenol) expressed by General Formula (4), thesubstitution position of the formyl group should desirably be the orthoposition or para position relative to the hydroxyl group. For example, acompound expressed by General Formula (13) or (14) specified below isdesirable.

(In the formula, R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3).)

(In the formula, R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3).)

Accordingly, specific compounds corresponding to a bis(formylphenol)expressed by the aforementioned General Formula (4) include thefollowing, for example:

-   4,4′-methylene bis(2-methyl-4-formylphenol),-   2,2′-methylene bis(4-methyl-6-formylphenol),-   4,4′-methylene bis(2-bromo-6-formylphenol),-   2,2-bis(3-formyl-4-hydroxy phenyl)propane,-   1,2-bis(3-formyl-4-hydroxy-5-methoxy phenyl)ethane,-   3,3′-dimethyl-5,5′-diformyl-4,4′-biphenol,-   1,3-bis(3-formyl-4-hydroxyphenyl)adamantane, and-   1,3-bis(3-formyl-5-methyl-4-hydroxyphenyl)adamantane

Under a production method conforming to the present invention, thetarget substance corresponding to the material, or a bis(formylphenol)expressed by General Formula (4), can be produced by causing a bisphenolexpressed by General Formula (3) to react with hexamethylene tetraminein the presence of an acid and then hydrolyzing the obtained reactionproduct.

(In the formula, all Rs may be the same or different and respectivelyrepresent a hydrogen atom or an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have an ether group, where n indicates aninteger of 0 or 1 to 3. Both R₁s may be the same or different andrespectively represent a hydrocarbon group, hydrocarbon group containingoxygen atom, halogenated hydrocarbon, hydroxyl group or halogen group. Xindicates a bivalent bond group or a single bond.)

Under a production method conforming to the present invention, thebisphenol expressed by the aforementioned General Formula (3)representing the direct material compound may be such that in theformula, R may be a hydrogen atom or an aliphatic hydrocarbon group thatmay have an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have an ether group, and X, R₁ and n indicatethe same things represented by the corresponding symbols in GeneralFormula (4). Accordingly, specifically X, R₁ and n may be the same as ordifferent from X, R₁ and n in the aforementioned General Formula (4),and for example, the substitution group of X or R₁ may be hydrolyzed aslong as the bisphenol skeletal can be maintained. However, it isdesirable that X and R₁ remain stable, or unchanged, during the courseof reaction.

Similarly with the bisphenol expressed by General Formula (3), acompound where the substitution position of the hydroxy methyl group oralkoxy methyl group is the ortho position or para position relative tothe hydroxyl group is desired.

On the other hand, R is a hydrogen atom or an aliphatic hydrocarbongroup that may have an aromatic hydrocarbon group, hydroxyl group, oraliphatic hydrocarbon group that may have an ether group, where thealiphatic hydrocarbon group that may have an aromatic hydrocarbon group,hydroxyl group, or aliphatic hydrocarbon group that may have an ethergroup, should desirably be a substituted or unsubstituted saturatedaliphatic hydrocarbon group such as an alkyl group, alkoxy alkyl groupor phenyl alkyl group, etc., where a primary or secondary substituted orunsubstituted alkyl group is desirable. This alkyl group may be an alkylgroup with a carbon atom number of 1 to 20, or desirably a methyl group,isopropyl group, n-butyl group or other alkyl group of straight orbranched chain with a carbon atom number of 1 to 10 or cycloalkyl groupwith a carbon atom number of 5 to 10.

As for bond group X, one having both hydroxy phenyl groups bonded on thesame carbon of bond group X is desirable, where specific examplesinclude compounds expressed by General Formulas (15) and (16) specifiedbelow, among others. When a bisphenol having such chemical structure isused as the material, the yield will increase compared to when the Duffreaction is used, which is desirable.

In the above formulas, R is the same as in General Formula (3), whereR₂′, R₃′ and R₄ are independent of each other and a hydrogen atom or thesame as R₁ in General Formula (3), while R₅ and R₆ are the same as amonovalent hydrocarbon group that can be substituted to a bivalenthydrocarbon group of bond group X, or a hydrogen atom.

Favorable forms of R₅ and R₆ are independent hydrogen atoms or alkylgroups with a carbon atom number of 1 to 10, cycloalkyl groups with acarbon atom number of 5 to 10, or alicyclic or crosslinked alkylidenegroup with a carbon atom number of 5 to 20 forming a ring containing thecarbon atoms of the bond group.

In the aforementioned General Formulas (15) and (16), it is desirablethat R₂′ have a substitution group, not hydrogen atom, for such reasonsas inexpensive material, high yield, ease of obtaining highly puresubstance via crystallization, etc.

In General Formula (16), it is desirable that at least one of R₅ and R₆be a hydrogen atom, because then in many cases a bisphenol being thematerial corresponding to a compound expressed by General Formula (16)can be obtained relatively easily by causing R₂′ to react with an alkylgroup-containing p-alkyl phenol and aldehyde in the presence of an acidcatalyst.

In General Formula (15), it is desirable that R₅ and R₆ be both hydrogenatoms and R₂′ be an alkyl group, because then a bis(hydroxymethylphenol)expressed by General Formula (15), being the direct material under thepresent invention and where R is hydrogen, can be obtained by causing aO-alkyl phenol being the material phenol to react with formaldehyde inthe presence of an alkali catalyst, without removing 4,4′-methylenebisphenol from the reactor.

This reaction formula is specified below.

Specific compounds corresponding to a bisphenol expressed by GeneralFormula (3), which is the material compound used in a production methodconforming to the present invention, include the following, for example:

-   4,4′-methylene bis(2-methyl-6-hydroxymethylphenol),-   4,4′-methylene bis(2-hydroxy methyl phenol),-   4,4′-methylene bis(2,5-dimethyl-6-hydroxymethylphenol),-   4,4′-methylene bis(2-methoxy-6-hydroxymethylphenol),-   2,2′-methylene bis(4-methyl-6-hydroxymethylphenol),-   2,2′-bis(3-methyl-4-hydroxy-5-hydroxymethylphenyl)propane,-   2,2′-bis(3-hydroxy methyl-4-hydroxyphenyl)propane,-   9,9-bis(3-phenyl-4-hydroxy-5-hydroxymethylphenyl)fluorenone,-   2,6-bis    {(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methyl}-4-methylphenol,-   2,6-bis    {(2,5-dimethyl-3-hydroxymethyl-4-hydroxyphenyl)methyl}-4-methylphenol,-   2,6-bis    {(3-methyl-4-hydroxy-5-hydroxymethylphenyl)methyl}-4-methylphenol,-   2,4-bis {(2,5-dimethyl-3-hydroxymethyl-4-hydroxy    phenyl)methyl}-3,6-dimethylphenol,-   Bis[3-(3-methyl-4-hydroxy-5-hydroxymethylphenyl)methyl-2,5-dimethyl-4-hydroxyphen    yl]methane,-   3,3′-dimethyl-5,5′-di(hydroxymethyl)-4,4′-biphenol,-   1,3-bis(3-methyl-4-hydroxy-5-hydroxymethylphenyl)adamantane,-   1,4-bis{1-(3-methyl-4-hydroxy-5-hydroxymethylphenyl)isopropyl}benzene,-   3,4-bis(3-hydroxy methyl-4-hydroxyphenyl)-3-hexene, and-   3,4-bis(3-hydroxy methyl-4-hydroxyphenyl)hexane

Also, under a production method conforming to the present invention, thetarget compound, or a polynuclear poly(formylphenol) expressed by theaforementioned General Formula (2), is a polynuclear poly(formylphenol)expressed by the aforementioned General Formula (8) and having three ormore hydroxy-substituted phenyl nuclei when, in the formula, m is aninteger of 0, 1 or 2, but when m is 0, X is a trivalent to hexavalentbond group and l+n is 3 to 6. Here, in the aforementioned GeneralFormula (8), X is a single bond or bivalent to hexavalent bond group,but when m is 0, X is a trivalent to hexavalent bond group. X shoulddesirably be a bivalent to tetravalent bond group. Such bivalent tohexavalent bond group is not specifically limited, as long as it is apolynuclear poly(formylphenol) to which a production method under thepresent invention can be applied. However, it may be a hydrocarbongroup, oxygen atom-containing group, sulfur atom-containing group,nitrogen atom-containing group, halogen atom-containing group, etc.Desired examples of the bivalent to hexavalent hydrocarbon group thatmay have a substitution group include a saturated or unsaturatedhydrocarbon group, polycyclic or monocyclic alicylcic hydrocarbon groupor aromatic hydrocarbon group of direct or branched chain with a carbonatom number of 1 to 30; condensed polycyclic hydrocarbon group such as9,9-fluorenylidene; crosslinked cyclic hydrocarbon group such asadamantane-2,3-diyl; spiro hydrocarbon group such asspiro[3.4]octa-7,8-diyl; polycyclic aggregated hydrocarbon group such asP-terphenyl-4,4″-diyl; terpene hydrocarbon group such as5-norbornene-2,3-diyl; and heterocyclic hydrocarbon group such as2,5-thiophendiyl.

The aforementioned bivalent to hexavalent hydrocarbon groups may havebivalent substitution groups or monovalent substitution groups that canact as a bond group.

Among the above, favorable choices for X include, for example, trivalentsaturated or unsaturated hydrocarbon groups expressed by the chemicalformulas specified below, methine group (Chemical Formula 3), ethylidynegroup (Chemical Formula 4), cyclohexane-1,1,4-tolyl group (ChemicalFormula 5), propylidine group (Chemical Formula 6), propane-1,2,3-tolylgroup, butane-1,3,3-tolyl group (Chemical Formula 7), and1,4,4-cyclohexane-1-en-tolyl group (Chemical Formula 8).

Examples include tetravalent saturated or unsaturated hydrocarbon groupsexpressed by the chemical formulas specified below,ethane-1,1,2,2-tetrayl group (Chemical Formula 9),1,1,4,4-cyclohexane-tetrayl group (Chemical Formula 10), methane tetraylgroup (Chemical Formula 11), ethylene diylidene group (Chemical Formula12), and 1,1,4,4-cyclohexane-2-en-tetrayl group (Chemical Formula 13).

For example, aromatic hydrocarbon groups, etc., expressed by thechemical formula specified below can be considered.

Furthermore, specific examples of bivalent to hexavalent bond groupswhen bond group X is an oxygen atom-containing group, sulfuratom-containing group, nitrogen atom-containing group or halogenatom-containing group include, among others, bivalent to hexavalentchain or cyclic compound groups having a hetero atom, such as a ketonegroup, ether group, oxocarbonyl group (carboxylate group), sulfidegroup, sulfoxide group, sulfone group, thioketone group, thiocarbonylgroup, carbonyl dioxy group, sulfonyl dioxy group, azo group, hydrazogroup, imino group, ureilene group or hydrocarbon group having halogenatom.

Also, Y indicates a bivalent alkylene group, or desirably a saturatedhydrocarbon group of straight or branched chain with a carbon atomnumber of 1 to 5.

Also, with respect to a polynuclear poly(formylphenol) expressed byGeneral Formula (9), R₁, R₂ and R₃ in the formula may be the same ordifferent, and respectively represent a hydrocarbon group, hydrocarbongroup containing oxygen atom, hydroxyl group, halogen group orhalogenated hydrocarbon group, while a and c respectively indicate aninteger of 0 or 1 to 3, and b indicates an integer of 0, 1 or 2.

Examples of such hydrocarbon group include a monovalent saturated orunsaturated hydrocarbon group, polycyclic or monocyclic alicylcichydrocarbon group or aromatic hydrocarbon group of direct or branchedchain that may have a substitution group.

Specific examples of the aforementioned monovalent hydrocarbon groupinclude, among others: monovalent noncyclic saturated hydrocarbon groupswith a carbon atom number of 1 to 30, or preferably 1 to 15, such asmethyl, ethyl, isopropyl, t-butyl, sec-butyl, isobutyl, t-octyl,n-dodecyl and other alkyl groups; monovalent noncyclic unsaturatedhydrocarbon groups such as vinyl, aryl, hexa-2,4-diene-1-yl andbuta-2-en-1-yl; monovalent monocyclic alicyclic hydrocarbon groups witha carbon atom number of 3 to 15, or preferably 5 to 7, such ascyclopentyl, cyclohexyl, 2-cyclohexe-3-yl and cyclohexa-2,5-diene-1-yl;monovalent monocyclic aromatic hydrocarbon groups such as phenyl and2-propyl-phenyl; polycyclic aromatic hydrocarbon groups such as1-naphthyl, phenanthrene-2-yl; monovalent condensed polycyclichydrocarbon groups such as indene-2-yl and fluorene-9-yl; monovalentcrosslinked cyclic hydrocarbon groups such as bicyclo[2.2.1]hepto-2-yl,6-ethyl bicyclo[2.2.1]hepto-2-yl,tetracyclo[4.4.0.1^(2.5).1^(7,10)]dodecene-3-yl and adamantane-2-yl;monovalent spiro hydrocarbon groups such as spiro[3.4]octa-7-yl;monovalent polycyclic aggregated hydrocarbon groups such as1,1′-biphenyl-4-yl, P-terphenyl-4-yl, 1,1′-diphenyl methane-4-yl andstilbene-4-yl; terpene hydrocarbon groups such as 2-pinene-10-yl and5-norbornene-2-yl; and monovalent heterocyclic hydrocarbon groups suchas furan-2-yl and 2H-pyran-2-yl.

The oxygen atom-containing hydrocarbon group is a hydrocarbon groupwhere one or more oxygen atoms bond in the chemical structure, wherespecific examples include, among others: substitution groups containinga methoxy, ethoxy, cyclohexyloxy or other alkoxy group, phenoxy or otheraryloxy group, 4-methoxy phenyl group, 2-methoxy phenyl group, furylgroup or other ether group; substitution groups containing a carbonylgroup such as an acetyl, propionyl, butyryl benzoyl or other acyl group;substitution groups containing a primary, secondary or tertiary estergroup such as an acryloyloxy, methacryloyloxy, acetoxy, benzoyloxy orother acyloxy group; substitution groups containing an hydroxyl groupsuch as 4-hydroxy phenyl, 4-hydroxy phenol methyl, 3-hydroxy-n-butyl or2-hydroxy ethyloxy; and monovalent heterocyclic hydrocarbon groups suchas furan-2-yl and 2H-pyran-2-yl.

Specific examples of the halogen group include, among others, a chlorineatom, bromine atom and fluorine atom. The halogenated hydrocarbon groupmay be a halogenated alkyl group such as a trifluoromethyl group.

Favorable forms of R₁, R₂ and R₃ are those having a carbon atom numberof 1 to 20 and an oxygen atom number of 0 to 2, and especially an alkylgroup with a carbon atom number of 1 to 10 or cycloalkyl group with acarbon atom number of 5 to 10 is desirable.

Also, the substitution positions of R₁, R₂ and R₃ may be the same ordifferent when a and c are 2 or 3, orb is 2.

Furthermore, l and n respectively indicate an integer of 1 to 3, while mindicates an integer of 0, 1 or 2. If m is 0, however, l+n is 3 to 6. Adesired combination of l, n and m is such that m is 0 and l+n is 3 or 4,or m is 1 and l and n are both 1. Also, substitution groups R₁ and R₃should desirably be the same and their substitution positions relativeto the OH group should also be the same. If m is 0, the OH group shoulddesirably be in position 4 relative to the bond position of bond group Xin the phenyl nucleus. If m is not 0, the OH group should desirably bein position 2 relative to the bond positions of bond groups X and Y inthe phenyl nucleus.

Also, with respect to a polynuclear poly(formylphenol) expressed byGeneral Formula (9), it is desirable that the substitution position ofthe formyl group be the ortho position or para position relative to thehydroxyl group.

Examples include compounds expressed by General Formulas (17), (18) and(19) specified below.

(In the formula, X is a trivalent bond group, R₁ and R₃ are methylgroups, a and c are both l, m is 0, and l+n is 3, according to GeneralFormula (9).)

(In the formula, X is a tetravalent bond group, R₁ and R₃ are methylgroups, a and c are both l, m is 0, and l+n is 4, according to GeneralFormula (9).)

(In the formula, X is a bivalent bond group, R₁, R₂ and R₃ are methylgroups, a, b and c are l, m is 0, and l+n is 1, according to GeneralFormula (9).)

Accordingly, specific compounds conforming to a polynuclearpoly(formylphenol) expressed by General Formula (9) include, forexample,1-[α-methyl-α-(3-formyl-5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-formyl-5-methy1-4-hydroxyphenyl)ethyl]benzene.

Under a production method conforming to the present invention, thetarget substance corresponding to the material, or a polynuclearpoly(formylphenol) expressed by General Formula (9), can be produced bycausing a polynuclear polyphenol expressed by General Formula (8) toreact with hexamethylene tetramine in the presence of an acid and thenhydrolyzing the obtained reaction product.

(In the formula, all Rs may be the same or different and respectivelyrepresent a hydrogen atom or an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have an ether group. R₁, R₂ and R₃ may be thesame or different and respectively represent a hydrocarbon group,hydrocarbon group containing oxygen atom, hydroxyl group, halogen groupor halogenated hydrocarbon group; a and c respectively indicate aninteger of 0 or 1 to 3, while b indicates an integer of 0, 1 or 2; l andn respectively indicate an integer of 1 to 3; m indicates an integer of0, 1 or 2; X indicates a bond group or a single bond; and Y indicates abivalent alkylene group. If m is 0, however, X is a trivalent tohexavalent bond group and l+n is 3 to 6.)

Under a production method conforming to the present invention, thetarget substance, or a polynuclear poly(formylphenol) expressed byGeneral Formula (9), is produced by causing the corresponding material,or a polynuclear polyphenol expressed by General Formula (8), to reactwith hexamethylene tetramine in the presence of an acid and thenhydrolyzing the obtained reaction product. This reaction converts thehydroxy methyl group or alkoxy methyl group in the polynuclearpolyphenol compound (the material compound) expressed by theaforementioned General Formula (8) and provides the target substance, ora polynuclear poly(formylphenol) compound expressed by General Formula(9).

Accordingly, with respect to a polynuclear poly(formylphenol) expressedby the aforementioned General Formula (8), l, m, n and Y in the formulamay be the same as the corresponding symbols in General Formula (9),while R₁, R₂, R₃, a, b, c and X may be the same as or different from thecorresponding symbols in General Formula (9). For example, if X has amonovalent group that undergoes acid decomposition, X may decomposeduring the reaction as long as the alkoxy methyl group or hydroxy methylgroup is formylated and the original polynuclear skeletal is maintained.R₁, R₂, R₃, a, b, c and X may not necessarily be the same as thecorresponding symbols in General Formula (9), but it is desirable thatthey be the same. R₁, R₂ and R₃ may be the same or different, andrespectively represent a hydrocarbon group, hydrocarbon group containingoxygen atom, hydroxyl group, halogen group or halogenated hydrocarbongroup, while a and c respectively indicate an integer of 0 or 1 to 3; bindicates an integer of 0, 1 or 2; l and n respectively indicate aninteger of 1 to 3; m indicates an integer of 0, 1 or 2; X indicates abond group or a single bond; and Y indicates a bivalent alkylene group.R represents a hydrogen atom or an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have an ether group. If m is 0, however, l+nis 3 to 6.

Specifically, R₁, R₂, R₃, a, b, c, l, m, n, X and Y are the same as whatis described above with respect to General Formula (9). Similarly, adesired combination of l, n and m is such that m is 0 and l+n is 3 or 4,or m is 1 and l and n are both 1. Also, substitution groups R₁, R₂ andR₃ should desirably be the same and their substitution positionsrelative to the OH group should also be the same. If m is 0, the OHgroup should desirably be in position 4 relative to the bond position ofbond group X in the phenyl nucleus. If m is not 0, the OH group shoulddesirably in position 2 relative to the bond positions of bond groups Xand Y in the phenyl nucleus. Specifically, R is the same as thecorresponding symbol in General Formula (3).

Also, with respect to a polynuclear polyphenol expressed by GeneralFormula (8), the substitution position of the hydroxy methyl group oralkoxy methyl group should desirably be the ortho position or paraposition relative to the hydroxyl group, and it is more desirable tohave a substitution group in other o-position or p-position of thehydroxyl group because it increases the yield of synthesis. However,cases where at least one of R₁ R₂ and R₃ in General Formula (8) is ahydrocarbon having a hydroxyl group, ether group or halogen group(bromine, chlorine, etc.,) in the α-position, or specifically a hydroxymethyl group or alkoxy methyl group having such characteristics, are notdesirable. Examples of a polynuclear polyphenol expressed by GeneralFormula (8) include, among others, compounds expressed by GeneralFormulas (20), (21) and (22) specified below.

(In the formula, X is a trivalent bond group, m is 0, and l+n is 3,according to General Formula (8).)

(In the formula, X is a tetravalent bond group, m is 0, and l+n is 4,according to General Formula (8).)

(In the formula, X is a bivalent bond group, m is 1, and l and n are 1,according to General Formula (8).)

On the other hand, R is a hydrogen atom or an aliphatic hydrocarbongroup that may have an aromatic hydrocarbon group, hydroxyl group, oraliphatic hydrocarbon group that may have an ether group, where thealiphatic hydrocarbon group that may have an aromatic hydrocarbon group,hydroxyl group, or aliphatic hydrocarbon group that may have an ethergroup, should desirably be a substituted or unsubstituted saturatedaliphatic hydrocarbon group such as an alkyl group, alkoxy alkyl groupor phenyl alkyl group, etc., where a primary or secondary substituted orunsubstituted alkyl group is desirable. This alkyl group may be an alkylgroup with a carbon atom number of 1 to 20, or desirably an alkyl groupof straight or branched chain with a carbon atom number of 1 to 10 orcycloalkyl group with a carbon atom number of 5 to 10. Specific examplesinclude methyl, ethyl and cyclohexyl, among others.

Accordingly, specific compounds corresponding to the material compoundused in a production method conforming to the present invention, or apolynuclear hydroxy methyl phenol or polynuclear alkoxy methyl phenolexpressed by General Formula (8), include the following, for example:

-   1-[α-methyl-α-(3-hydroxymethyl-5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-hydrox    ymethyl-5-methyl-4-hydroxyphenyl)ethyl]benzene,-   1-[α-methyl-α-(3-methoxymethyl-5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-methox    ymethyl-5-methyl-4-hydroxyphenyl)ethyl]benzene, and-   1-[α-methyl-α-(3-butoxymethyl-5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-butoxym    ethyl-5-methyl-4-hydroxyphenyl)ethyl]benzene

By using a production method conforming to the present invention, ahydroxy methyl group or alkoxy methyl group bonding with an aromaticring can be formylated without using the Duff reaction, which is aconventional method known to introduce a formyl group to an aromaticring and where an unsubstituted benzene ring is directly formylated.Although the mechanism of this reaction is not clear, it is estimatedthat Schiff's base or other base is generated as an intermediateproduct, which is then formylated through hydrolysis.

A production method conforming to the present invention, pertaining toan example where 4,4′-methylene bis(2-methyl-6-hydroxymethylphenol) iscaused to react with hexamethylene tetramine in the presence of an acidand the obtained reaction product is hydrolyzed to produce4,4′-methylene bis(2-methyl-6-formylphenol), is expressed by ReactionFormula (2) specified below.

Also, an example where

-   1-[α-methyl-α-(3-hydroxymethyl-5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-hydrox    ymethyl-5-methyl-4-hydroxyphenyl)ethyl]benzene (Chemical Formula 15)    is caused to react with hexamethylene tetramine in the presence of    an acid and the obtained reaction product is hydrolyzed to produce-   1-[α-methyl-α-(3-formyl-5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-formyl-5-methy    1-4-hydroxyphenyl)ethyl]benzene (Chemical Formula 16), is expressed    by Reaction Formula (3) specified below.

Under a production method conforming to the present invention, where apolynuclear poly(hydroxymethylphenol) or polynuclearpoly(alkoxymethylphenol) expressed by the aforementioned General Formula(1) is caused to react with hexamethylene tetramine in the presence ofan acid, acids that can be used include: hydrochloric acid, sulfuricacid, phosphoric acid and other mineral acids; p-toluene sulfonic acidand other organic sulfonic acids; clay, acid clay, zeolite and othersilica-alumina solid catalysts; tin chloride, iron chloride, boronfluoride and other Lewis acids; acetic acid, formic acid, oxalic acid,benzoic acid and other aliphatic or aromatic organic carbonic acids aswell as trifluoroacetic acids, trichloroacetic acids, tribromoaceticacid, monofluoroacetic acid, monochloro acetic acid, fluorobenzoic acidand other halogenated organic carbonic acids; and boric acid and otherinorganic weak acids.

Among the above, organic carbonic acids and boric acids are desirable,of which liquid halogenated organic carbonic acids are particularlydesirable.

The amount of acid used in the reaction is affected by the type of acid,and specifically the range of amounts of acid to be added and theoptimal amount of acid vary accordingly. Normally, however, around 0.1to 100 mols, or preferably around 1 to 50 mols, of acid is addedrelative to 1 mol of polynuclear poly(hydroxymethylphenol) orpolynuclear poly(alkoxymethylphenol). For example, if the polynuclearpoly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol) is abisphenol expressed by the aforementioned General Formula (3), andtrifluoroacetic acid is used, then the amount of trifluoroacetic acidshould be in a range of around 1 to 30 mols, or preferably in a range of5 to 20 mols, relative to 1 mol of bisphenol.

In another example where the polynuclear poly(hydroxymethylphenol) orpolynuclear poly(alkoxymethylphenol) expressed by the aforementionedGeneral Formula (1) is a polynuclear poly(hydroxymethylphenol) orpolynuclear poly(alkoxymethylphenyl) having three or morehydroxy-substituted phenyl nuclei as expressed by the aforementionedGeneral Formula (8), and trifluoroacetic acid is used, then the amountof trifluoroacetic acid should be in a range of (l+m+n)×0.5 mols to(l+m+n)×15 mols, or preferably in a range of around (l+m+n)×2.5 mols to(l+m+n)×10 mols, relative to 1 mol of polynuclearpoly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol). If(l+m+n) is 3, for example, the aforementioned preferable range is from7.5 mols to 30 mols. If (l+m+n) is 4, the preferable range is from 10mols to 40 mols.

Also, the form of hexamethylene tetramine is not limited, and it can bea hexamethylene tetramine produced by adding ammonia and formaldehyde,both of which are materials for producing hexamethylene tetramine, inthe reaction matrix. The amount of hexamethylene tetramine is notspecifically limited as long as it is equivalent to or greater than thetotal mols of l+m+n in the formula relative to 1 mol of polynuclearpoly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol).However, adding hexamethylene tetramine excessively reduces thevolumetric efficiency, and thus normally, the amount of hexamethylenetetramine should be in a range of 10 mols or less, or preferably in arange of (l+m+n)×1.05 mols to (l+m+n)×1.5 mols.

For example, if the polynuclear poly(hydroxymethylphenol) or polynuclearpoly(alkoxymethylphenol) is a bisphenol expressed by the aforementionedGeneral Formula (3), then the amount of hexamethylene tetramine is notspecifically limited as long as it is 2 mols or more relative to 1 molof bisphenol. However, adding hexamethylene tetramine excessivelyreduces the volumetric efficiency, and thus normally its amount shouldbe in a range of 2 to 10 mols, or preferably in a range of 2 to 5 mols,or more preferably in a range of 2.1 to 3 mols.

In another example where the polynuclear poly(hydroxymethylphenol) orpolynuclear poly(alkoxymethylphenol) is a polynuclearpoly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenyl) havingthree or more hydroxy-substituted phenyl nuclei as expressed by theaforementioned General Formula (8), and (l+m+n) is 3, then the amount ofhexamethylene tetramine should be in a range of 3.1 to 4.5 mols. If(l+m+n) is 4, it should be in a range of 4.2 to 6 mols.

A solvent may or may not be used in the reaction. A solvent is notparticularly necessary as long as the reaction materials are dissolvedand the reaction composition can be agitated. If the acid or anymaterial used has a high melting point, or the reaction liquid has highviscosity at the reaction temperature, or otherwise agitation isdifficult, it is desirable to use a solvent.

The solvent to be used is not specifically limited as long as it doesnot inhibit the reaction. Examples include: ether, diethyl ether,tetrahydrofuran and other chain or cyclic aliphatic ethers; ethylacetate, n-butyl acetate and other desirably primary or secondaryaliphatic esters; methanol, ethanol, butanol and other low-gradealiphatic alcohols with a carbon number of 1 to 4; cyclohexanol andother alicyclic alkyl alcohols; toluene, xylene, ethyl benzene and otheraromatic hydrocarbons; and mixtures thereof. Among others, aromatichydrocarbons are desirable.

As for the reaction, the method or order in which to introduce thereaction materials are not limited, and any method or order can beselected as deemed appropriate according to the properties, etc., of thematerials used. For example, the material, or a polynuclearpoly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol)expressed by the aforementioned General Formula (1), can be added to asolution where the acid, hexamethylene tetramine and solvent cancoexist; or the acid and hexamethylene tetramine can be added to asolution where the polynuclear poly(hydroxymethylphenol) or polynuclearpoly(alkoxymethylphenol) and solvent can coexist; or the acid can beadded to a solution where the polynuclear poly(hydroxymethylphenol) orpolynuclear poly(alkoxymethylphenol), hexamethylene tetramine andsolvent can coexist. If any organic carbonic acid is used as the acid,it is desirable to add the material, or polynuclearpoly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol), to asolution where the organic carbonic acid and hexamethylene tetraminecoexist.

The reaction temperature and pressure are not specifically limited aslong as the reaction can progress smoothly, but the reaction temperatureis normally in a range of −50 to 150° C., or preferably in a range of 0to 110° C., or more preferably in a range of 50 to 90° C. The reactionpressure is in a range of slight decompression to slight pressurization,and preferably around a normal pressure.

Under a production method conforming to the present invention, thetarget substance, or a polynuclear poly(formylphenol) expressed by theaforementioned General Formula (2), is obtained by causing a polynuclearpoly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol)expressed by the aforementioned General Formula (1) to react withhexamethylene tetramine in the presence of an acid and then hydrolyzingthe obtained intermediate reaction product.

In the hydrolysis reaction, the intermediate reaction product obtainedfrom the reaction with hexamethylene tetramine may be separated by meansof filtering, etc., or refined further as necessary. From the viewpointof improved efficiency and yield of reaction, however, it is desirableto directly use the aforementioned mixture obtained by the reaction withhexamethylene tetramine. Also, a catalyst may or may not be used in thereaction, but desirably a catalyst should be used. The catalyst to beused may be an acid catalyst or alkali catalyst. If the material, or apolynuclear poly(hydroxymethylphenol) or polynuclearpoly(alkoxymethylphenol) expressed by the aforementioned General Formula(1), contains primary ester in its phenyl nucleus or bond group X, thenuse of an acid catalyst is desirable because the material is easy tohydrolyze in the presence of an alkali. It is also possible, forexample, to use the same acid employed in the reaction withhexamethylene tetramine directly as the catalyst for hydrolysis. In thiscase, more acid may be added if the reaction is slow.

Or, any known acid catalyst may be added on top of the aforementionedacid. However, exercise caution because in the case of a strong acid,adding it excessively will cause the formyl group or ester group tobreak down and the yield will drop.

The amount of acid to be used should normally be in a range of 0.1 to100 mols, or preferably in a range of around 1 to 20 mols, relative to 1mol of polynuclear poly(hydroxymethylphenol) or polynuclearpoly(alkoxymethylphenol) expressed by the aforementioned General Formula(1).

Accordingly, examples of the acid catalyst that can be used inhydrolysis include: hydrochloric acid, sulfuric acid and other mineralacids; p-toluene sulfonic acid and other organic sulfonic acids; andphosphoric acid, acetic acid, formic acid, trifluoroacetic acid andother organic carbonic acids. Examples of the alkali catalyst that canbe used in hydrolysis include: sodium hydroxide, potassium hydroxide andother inorganic bases; and tetramethyl ammonium hydroxide and otherorganic bases.

At the time of hydrolysis reaction, the amount of water in the reactioncomposition is not specifically limited as long as the reaction canprogress smoothly. From the viewpoint of volumetric efficiency, etc.,however, the amount of water should normally be in a range of (l+m+n)×1mols to (l+m+n)×40 mols, or preferably in a range of (l+m+n)×10 mols to(l+m+n)×25 mols, relative to 1 mol of the material polynuclearpoly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol)expressed by the aforementioned General Formula (1). If the polynuclearpoly(hydroxymethylphenol) or polynuclear poly(alkoxymethylphenol) is abisphenol expressed by the aforementioned General Formula (3), forexample, the amount of water is normally in a range of 2 to 80 mols, orpreferably in a range of 20 to 50 mols, relative to 1 mol of thematerial bisphenol.

The reaction temperature and pressure are not specifically limited aslong as the reaction can progress smoothly, but the reaction temperatureis normally in a range of −50 to 150° C., or preferably in a range of 0to 100° C., or more preferably in a range of 50 to 80° C. The reactionpressure is in a range of slight decompression to slight pressurization,and preferably around a normal pressure.

After the reaction, according to known methods, the target compositionor refined product may be collected at high yield from the mixtureobtained from the reaction. If the target substance in the mixtureobtained from the reaction has precipitated as crystal, for example,then the target substance may be filtered out directly. If the targetsubstance has not precipitated as crystal, then a poor solvent may beadded to the mixture obtained from the reaction to precipitate andseparate the target substance.

At this time, neutralization using alkali water of the acid catalyst inthe mixture obtained from the reaction, or neutralization of the acidusing an alkali catalyst, is not always required. If an acid catalyst isused, for example, it is possible to add to the mixture obtained fromthe reaction an appropriate amount of sodium hydroxide or other alkaliwater needed to neutralize the acid catalyst until the pH becomesapprox. 4 to 7, and then perform the aforementionedseparation/precipitation operation of the target substance, such asadding a solvent that can be separated from water, such as toluene,xylene, methyl isobutyl ketone or ether, to cause the water layer toseparate from the oil layer containing the target substance. Or, thetarget substance may be precipitated and separated without neutralizingthe acid catalyst in the mixture obtained from the reaction, followed bywashing of the obtained target composition to remove the acid.

Particularly when the acid used in the reaction is trifluoroacetic acidor other acid of low boiling point, the latter method lets you distilland collect the acid catalyst in the mixture obtained from the reactionbecause the acid catalyst has not been neutralized, and utilize thecollected acid catalyst directly.

If necessary in refining the target substance, after the aforementionedoperation the obtained target composition may be further mixed withwater or toluene, xylene, methyl isobutyl ketone, ether or other solventthat can be separated from water to dissolve the target composition,after which the water layer can be separated and oil layer washed inorder to obtain the oil layer containing the target substance.

Next, the solvent is distilled away from the obtained oil layer, andthen a crystallization solvent is added to crystallize the targetsubstance and filter out the crystal. If the purity of the crystal islow, the aforementioned recrystallization operation may be repeated onceor multiple times as necessary.

The polynuclear polyphenol expressed by General Formula (1), used as thedirect material in a production method conforming to the presentinvention, is not specifically limited in terms of how it is produced.However, if, for example, the polynuclear poly(hydroxymethylphenol) orpolynuclear poly(alkoxymethylphenol) expressed by the aforementionedGeneral Formula (1) is a bisphenol expressed by the aforementionedGeneral Formula (3), then the material can be easily obtained from abisphenol expressed by General Formula (5) specified below by means ofany known hydroxy methylation reaction or alkoxy methylation reaction,among others.

(In the formula, R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3).)

Examples of the reaction product include a bis(hydroxymethylphenol)expressed by General Formula (6) specified below, being a bisphenolexpressed by General Formula (3) where R is a hydrogen atom.

(In the formula, R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3).)

If the bisphenol is 4,4′-methylene bis(2-methylphenol), the bisphenolcan be caused to react with formaldehyde in the presence of an alkalicatalyst, as illustrated by Reaction Formula (4) specified below. It iseconomically desirable to use as the materials those compounds that canbe produced easily from inexpensive materials such as formaldehyde andalkali. It is more desirable to use a material bisphenol whose hydroxylgroup has no substitution group in only one of the o-position andp-position, and has a substitution group in all other positions, becauseit will increase the yield and facilitate production of the targetsubstance at high purity.

Also, the bis(alkoxymethylphenol) can be produced easily by causing theobtained bis(hydroxymethylphenol) to further react with an alcoholexpressed by General Formula (7) specified below in the presence of anacid catalyst, as illustrated by Reaction Formula (5) specified below.As for the alcohol expressed by General Formula (7), primary orsecondary alcohol is desirable, such as methanol, n-butanol, methoxyethanol, ethylene glycol, etc.

[Chemical 40]R—OH  General Formula (7)(In the formula, R represents an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have an ether group.)

(In the formula, R represents an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have an ether group.)

Also, if the polynuclear poly(hydroxymethylphenol) or polynuclearpoly(alkoxymethylphenol) expressed by the aforementioned General Formula(1) is a polynuclear poly(hydroxymethylphenol) or polynuclearpoly(alkoxymethylphenyl) having three or more hydroxy-substituted phenylnuclei as expressed by the aforementioned General Formula (8), thematerial can be easily obtained from a polynuclear polyphenol expressedby General Formula (10) specified below by means of any known hydroxymethylation reaction or alkoxy methylation reaction, among others.

(In the formula, R₁, R₂, R₃, a, b, c, l, m, n, X and Y indicate the samethings represented by the corresponding symbols in General Formula (8),and at least one of the o-position and p-position of the hydroxyl groupis not substituted.)

As for the reaction product, if R is a hydrogen atom in the polynuclearpolyphenol expressed by the aforementioned General Formula (8), forexample, then the polynuclear poly(hydroxymethylphenol) is expressed byGeneral Formula (11) specified below.

(In the formula, R₁, R₂, R₃, a, b, c, l, m, n, X and Y indicate the samethings represented by the corresponding symbols in General Formula (8),and the substitution position of the hydroxy methyl group is theopposition or p-position relative to the hydroxyl group.)

Such polynuclear poly(hydroxymethylphenol) can be produced easily by anyknown method, such as the method described in Japanese Patent Laid-openNo. 2003-300922 whereby a polynuclear polyphenol is caused to react withformaldehyde in the presence of an alkali catalyst. For example,Reaction Formula (6) specified below illustrates an example where thepolynuclear polyphenol is1-[α-methyl-α-(5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(5-methyl-4-hydroxyphenyl)ethyl]benzene.It is economically desirable to use as the materials those compoundsthat can be produced easily from inexpensive materials such asformaldehyde and alkali. It is more desirable to use a materialpolynuclear polyphenol, expressed by General Formula (10), whosehydroxyl group has a hydrogen atom in only one of the substitutiongroups corresponding to the opposition and p-position, because it willincrease the yield and facilitate production of the target substance athigh purity.

On the other hand, the polynuclear poly(alkoxymethylphenol) can beproduced easily by, for example, causing the polynuclearpoly(hydroxymethylphenol) obtained above to further react with analcohol expressed by General Formula (12) specified below in thepresence of an acid catalyst. The desirable alcohols expressed byGeneral Formula (12), and specific examples, are the same as thosediscussed in relation to General Formula (7). Reaction Formula (7)specified below illustrates an example of such production method, wherethe polynuclear poly(hydroxymethylphenol) obtained from Reaction Formula(6) specified below is a tri(hydroxymethyl) compound or specifically1-[α-methyl-α-(3-hydroxymethyl-5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-hydroxy methyl-5-methyl-4-hydroxy phenyl)ethyl]benzene.

(In the formula, R represents an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have an ether group.)[Chemical 46]R—OH  General Formula (12)(In the formula, R represents an aliphatic hydrocarbon group that mayhave an aromatic hydrocarbon group, hydroxyl group, or aliphatichydrocarbon group that may have an ether group.)

Also, under a production method conforming to the present invention, theselection of whether to use a polynuclear poly(hydroxymethylphenol) orpolynuclear poly(alkoxymethylphenol) corresponding to the targetcompound is not specifically limited when a polynuclear polyphenolexpressed by General Formula (1) is used as the starting material. Adesired material can be determined as deemed appropriate by consideringthe production method, ease of achieving high purity, stability andtoxicity of the compound, reaction selectivity, and the like.

EFFECTS OF THE INVENTION

According to a production method conforming to the present invention, apolynuclear formyl phenol which is useful as a resist material,polymerization catalyst or resin or other material can be produced withease and at high yield and high volumetric efficiency by causing apolynuclear polyphenol expressed by General Formula (1) to react withhexamethylene tetramine in the presence of an acid and then hydrolyzethe reaction product.

Furthermore, the material polynuclear poly(hydroxymethylphenol) orpolynuclear poly(alkoxymethylphenol) can be produced easily from thecorresponding polynuclear polyphenol depending on the substitutionposition of the hydroxy methyl group or alkoxy methyl group as well asthe details of substitution numbers a, b, c and substitution groups R₁,R₂, R₃, X and Y, which allows for production of a polynuclearpoly(formylphenol) consistently from a polynuclear polyphenol in anindustrial setting with ease and at high yield and high efficiency.

BEST MODE FOR CARRYING OUT THE INVENTION EXAMPLES Example 1 Synthesis of4,4′-methylene bis(2-methyl-6-formylphenol) (Chemical Formula 17)

1140.0 g (10.0 mols) of trifluoroacetic acid was put in a four-way flaskwith a capacity of 5 liters and the reaction container was substitutedby nitrogen, after which 315.0 g (2.25 mols) of hexamethylene tetraminewas added at a temperature of approx. 30° C., and then 288.0 g of4,4′-methylene bis(2-methyl-6-hydroxymethylphenol) (1.0 mol; purity 93%based on high-speed liquid chromatograph (HPLC)) was added underagitation over 3 hours at a temperature of 40° C. to cause reaction.After the entire amount of the material had been added, the temperaturewas raised to 85° C., and then the mixture was further agitated for 3hours as a post-reaction. After the reaction, the obtained liquid waspartially collected and hydrolyzed, and then analyzed based on HPLC. Asa result, the main component that appeared to be the target substancehad a composition ratio of 70%. Next, 800.0 g of water was added to theliquid obtained from the reaction to implement hydrolysis reaction for 1hour at a temperature of 60° C. Crystal precipitated during thisreaction. After the reaction, 1471.0 g of 16% aqueous sodium hydroxidesolution was added to neutralize the obtained mixture liquid, and then50 g of methyl isobutyl ketone and 50 g of methanol were added further,after which the mixture was cooled and precipitated crystal was filteredout to obtain 302.3 g of a composition. The obtained composition was putin a four-way flask with a capacity of 2 liters, and 369.2 g of methylisobutyl ketone and 255.6 g of toluene were added, and then the mixturewas maintained at a temperature of 70° C. and agitated for 30 minutes ina slurry state. The mixture was cooled and precipitated crystal wasfiltered out and dried to obtain 196.8 g of yellow powder crystal havinga purity of 95.8% based on HPLC. The yield with respect to4,4′-methylene bis(2-methyl-6-hydroxymethylphenol) was 69.3%. Based onthe results of NMR and mass spectrometry, the obtained crystal wasconfirmed to be the target substance.

Melting point: 155.4° C. (based on peak top by differential scanningcalorimetry)

Molecular weight: 283 (M—H)⁻ (by mass spectrometry LC-MS (APCI⁻))

Proton NMR identification result (400 MHz, solvent: DMSO-d6, internalstandard: tetramethyl silane)

TABLE 1 Shift value (ppm) Proton number Signal Attribution 2.17 6 s —CH₃3.86 2 s —CH₂— 7.37 to 7.44 4 m Ph—H 10.00 2 s Ph—OH 10.88 2 s —CHO

Example 2 Synthesis of 2,2′-methylene bis(4-methyl-6-formylphenol) frombis(hydroxymethylphenol) Compound (Chemical Formula 18)

546.4 g (4.8 mols) of trifluoroacetic acid was put in a four-way flaskwith a capacity of 2 liters and the reaction container was substitutedby nitrogen, after which 123.2 g (0.88 mol) of hexamethylene tetraminewas added at a temperature of approx. 30° C., and then 115.3 g of2,2′-methylene bis(4-methyl-6-hydroxymethylphenol) (0.4 mol; purity 89%based on HPLC) was added under agitation over 2 hours at a temperatureof 60° C. to cause reaction. After the entire amount of the material hadbeen added, the temperature was raised to 85° C., and then the mixturewas further agitated for 4 hours as a post-reaction. After the reaction,the obtained mixture liquid was partially collected and then analyzedbased on HPLC in the same manner as in Example 1. As a result, the maincomponent that appeared to be the target substance had a compositionratio of 76%.

Next, 320.0 g of water was added to the liquid obtained from thereaction to implement hydrolysis reaction for 1 hour at a temperature of60° C. Crystal precipitated during this reaction. After the reaction,830.0 g of 16% aqueous sodium hydroxide solution was added to neutralizethe obtained mixture liquid, and then 220.0 g of toluene and 280.0 g ofcyclohexane were added further, after which the mixture was cooled andprecipitated crystal was filtered out and dried to obtain 81.5 g ofyellow powder having a purity of 95.6% based on HPLC. The yield withrespect to 2,2′-methylene bis(4-methyl-6-hydroxymethylphenol) was 71.7%.

Based on the results of NMR and mass spectrometry, the obtained crystalwas confirmed to be the target substance.

Melting point: 160.3° C., 168.5° C. (based on peak top by differentialscanning calorimetry)

Molecular weight: 283 (M—H)⁻ (by mass spectrometry LC-MS (APCI⁻))

Proton NMR identification result (400 MHz, solvent: DMSO-d6, internalstandard: tetramethyl silane)

TABLE 2 Shift value (ppm) Proton number Signal Attribution 2.23 6 s —CH₃3.90 2 s —CH₂— 7.20 to 7.44 4 m Ph—H 9.98 2 s Ph—OH 10.96 2 s —CHO

Example 3 Synthesis of 2,2′-methylene bis(4-methyl-6-formylphenol) frombis(alkoxymethylphenol) Compound

13.7 g (0.12 mol) of trifluoroacetic acid was put in a four-way flaskwith a capacity of 200 ml and the reaction container was substituted bynitrogen, after which 2.8 g (0.02 mol) of hexamethylene tetramine wasadded at a temperature of 30° C., and then 6.3 g of 2,2′-methylenebis(4-methyl-6-methoxymethylphenol) (0.01 mol; purity 90% based on HPLC)was added under agitation over 2 hours at a temperature of 60° C. tocause reaction. After the entire amount of the material had been added,the temperature was raised to 85° C., and then the mixture was furtheragitated for 4 hours as a post-reaction. After the reaction, theobtained liquid was partially collected and analyzed based on HPLC inthe same manner as in Example 2. As a result, the main componentcorresponding to the target substance had a composition ratio (area %)of 73%.

Example 4 Synthesis of 4,4′-methylene bis(2,5-dimethyl-6-formylphenol)(Chemical Formula 17)

171.0 g (1.5 mol) of trifluoroacetic acid was put in a four-way flaskwith a capacity of 1 liter and the reaction container was substituted bynitrogen, after which 47.3 g (0.34 mol) of hexamethylene tetramine wasadded at a temperature of approx. 25° C., and then 47.4 g (0.15 mol) of4,4′-methylene bis(2,5-dimethyl-6-hydroxymethylphenol) was added underagitation over 2.5 hours at a temperature of 50° C. to cause reaction.After the entire amount of the material had been added, the temperaturewas raised to 80° C., and then the mixture was further agitated for 20hours as a post-reaction. Next, 150.0 g of water was added to themixture liquid obtained from the reaction to implement hydrolysisreaction for 1 hour at a temperature of 70° C. (crystal precipitatedduring this reaction). 245.7 g of 16% aqueous sodium hydroxide solutionwas added to neutralize the obtained mixture liquid, which was then keptat a temperature of 80° C. for 1 hour. Thereafter, the mixture wascooled and precipitated crystal was filtered out to obtain 72.3 g ofcoarse crystal. Next, the obtained coarse crystal was put in a four-wayflask with a capacity of 1 liter, and then 70.0 g of methyl isobutylketone and 50.0 g of toluene were added and the mixture was kept at atemperature of 80° C. for 1 hour (the solution was in a slurry state),after which the mixture was cooled and precipitated crystal was filteredout and dried to obtain 45.3 g of yellow powder having a purity of 94.6%based on HPLC.

The yield with respect to 4,4′-methylenebis(2,5-dimethyl-6-hydroxymethylphenol) was 82.1%.

Based on the results of NMR and mass spectrometry, the obtained crystalwas confirmed to be the target substance.

Melting point: 200.7° C. (based on peak top by differential scanningcalorimetry)

Molecular weight: 311 (M—H)⁻ (by mass spectrometry LC-MS (APCI⁻))

Proton NMR identification result (400 MHz, solvent: DMSO-d6, internalstandard: tetramethyl silane)

TABLE 3 Shift value (ppm) Proton number Signal Attribution 2.07 6 s —CH₃([2]) 2.46 6 s —CH₃ ([1]) 3.84 2 s —CH₂ 7.00 2 s Ph—H 10.41 2 s Ph—OH12.25 2 s —CHO

Comparative Example 1 Synthesis of 4,4′-methylenebis(2-methyl-6-formylphenol) from 4,4′-methylene bis(2-methylphenol) viaDuff Reaction (Reaction Formula 8)

13.7 g (0.12 mol) of trifluoroacetic acid was put in a four-way flaskwith a capacity of 200 ml and the reaction container was substituted bynitrogen, after which 2.8 g (0.02 mol) of hexamethylene tetramine wasadded at a temperature of approx. 30° C., and then 2.3 g (0.01 mol) of4,4′-methylene bis(2-methylphenol) was added under agitation over 2hours at a temperature of 40° C. to cause reaction. After the entireamount of the material had been added, the temperature was raised to 85°C., and then the mixture was further agitated for 3 hours as apost-reaction. After the post-reaction, the obtained liquid waspartially collected and analyzed based on HPLC in the same manner as inExample 1. As a result, the main component that appeared to be thetarget substance had a low selectivity. When the post-reaction wascontinued for 12 hours and the obtained liquid was analyzed based onHPLC in the same manner, the main component that appeared to be thetarget substance had a composition ratio (area %) of only 7%.

Example 5 Synthesis of1-[α-methyl-α-(3-formyl-5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-formyl-5-methy1-4-hydroxyphenyl)ethyl]benzene

410.4 g (3.6 mol) of trifluoroacetic acid was put in a four-way flaskwith a capacity of 1 liter and the reaction container was substituted bynitrogen, after which 92.4 g (0.66 mol) of hexamethylene tetramine wasadded at a temperature of approx. 30° C., and then 111.4 g of1-[α-methyl-α-(3-hydroxymethyl-5-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-hydroxymethyl-5-methyl-4-hydroxyphenyl)ethyl]benzene (0.2 mol; purity 92.4%based on high-speed liquid chromatography (HPLC)) was added underagitation over 2 hours at a temperature of 60° C. to cause reaction.After the entire amount of the material had been added, the temperaturewas raised to 85° C., and then the mixture was further agitated for 5hours as a post-reaction.

Next, 240 g of water was added to the mixture liquid obtained from thereaction to implement hydrolysis reaction for 1 hour at a temperature of60° C. Viscous solids precipitated during this reaction. After thereaction, 220 g of toluene was added to the obtained mixture liquid,which was then heated to a temperature of 70° C. to dissolve the solidsand then kept stationary for 10 minutes to separate the water layer.32.8 g of 16% aqueous sodium hydrochloride solution was added toneutralize the obtained oil layer, and water was added further toagitate the mixture, which was then kept stationary to separate thewater layer and the obtained oil layer was decompressed and condensed upto 10 kPa at 70° C. Thereafter, 30 g of ethyl acetate was added and themixture was cooled to 50° C., and then 200 g of cyclohexane was addedfurther, with the mixture cooled and precipitated crystal filtered outand dried to obtain 52.7 g of light yellow powder (purity 93.2% based onhigh-speed liquid chromatography). Based on the results of NMR and massspectrometry, the obtained crystal was confirmed to be the targetsubstance.

Melting point (peak top by differential scanning calorimetry): 143.0° C.

Molecular weight: 549 (M—H)⁻ (by mass spectrometry LC-MS (APCI⁻))

Proton nuclear magnetic resonance analysis method (400 MHz, solvent:DMSO-d6)

TABLE 4 1H-NMR (400 MHz) measurement results (Internal standard:Tetramethyl silane) Shift value (ppm) Proton number Signal Attribution1.64 6 s —CH₃ ([1]) 2.11 3 s —CH₃ ([2]) 2.14 9 s —CH₃ ([3]) 6.98 to 7.5310 m Ph—H 9.94 2 s Ph—OH ([4]) 10.02 1 s Ph—OH ([5]) 10.92 3 s —CHO

Example 6

2.85 g (0.025 mol) of trifluoroacetic acid was put in a four-way flaskwith a capacity of 100 ml and the reaction container was substituted bynitrogen, after which 0.64 g (0.0046 mol) of hexamethylene tetramine wasadded at a temperature of 30° C., and then 0.77 g of1-[α-methyl-α-(3-hydroxymethyl-5-methyl-4-hydroxyphenyl)ethyl]4-[α,α-bis(3-hydroxymethyl-5-methyl-4-hydroxyphenyl)ethyl]benzene (0.00139 mol; purity92.4% based on high-speed liquid chromatography) was added underagitation over 5 minutes at a temperature of 50° C. to cause reaction.After the entire amount of the material had been added, 2.85 g oftoluene was added and the temperature was raised to 85° C., and then themixture was further agitated for 4 hours as a post-reaction. After thereaction, the obtained liquid was partially collected and hydrolyzed,and then analyzed by high-speed liquid chromatography. As a result, themain component that appeared to be the target substance had acomposition ratio (area ratio) of 60.9%.

Comparative Example 2

2.85 g (0.025 mol) of trifluoroacetic acid was put in a four-way flaskwith a capacity of 100 ml and the reaction container was substituted bynitrogen, after which 0.64 g (0.0046 mol) of hexamethylene tetramine wasadded at a temperature of 30° C., and then 0.65 g of1-[α-methyl-α-(3-methyl-4-hydroxyphenyl)ethyl]-4-[α,α-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene(0.00139 mol; purity 97.6% based on HPLC) was added under agitation over5 minutes at a temperature of 50° C. to cause reaction. After the entireamount of the material had been added, 2.85 g of toluene was added andthe temperature was raised to 85° C., and then the mixture was furtheragitated for 4 hours. However, a lot of material crystal remainedundissolved, and therefore the mixture was agitated further for 4 hoursas a post-reaction. After the reaction, the obtained liquid waspartially collected and hydrolyzed, and then analyzed by high-speedliquid chromatography. As a result, although the material had almostentirely reacted, the main component that appeared to be the targetsubstance had a composition ratio (area ratio) of 18.4%.

1. A method for producing a polynuclear poly(formylphenol) expressed byGeneral Formula (2), characterized in that a polynuclear polyphenolexpressed by General Formula (1) is caused to react with hexamethylenetetramine in the presence of an acid, and then the obtained reactionproduct is hydrolyzed:

wherein all Rs may be the same or different and respectively represent ahydrogen atom or an aliphatic hydrocarbon group that may have anaromatic hydrocarbon group, hydroxyl group, or aliphatic hydrocarbongroup that may have an ether group; R₁, R₂ and R₃ may be the same ordifferent and respectively represent a hydrocarbon group, hydrocarbongroup containing oxygen atom, hydroxyl group, halogen group orhalogenated hydrocarbon group; a and c respectively indicate an integerof 0 or 1 to 3, while b indicates an integer of 0, 1 or 2; l and nrespectively indicate an integer of 1 to 3; m indicates an integer of 0,1 or 2; X indicates a bond group or single bond; and Y indicates abivalent alkylene group;

wherein R₁, R₂, R₃, a, b, c, l, m, n, X and Y indicate the same thingsrepresented by the corresponding symbols in General Formula (1), whereinthe CH₂OR's in General Formula (1) are converted into the CHO's inGeneral Formula (2).
 2. The method for producing a polynuclearpoly(formylphenol) according to claim 1, wherein, with respect to apolynuclear polyphenol expressed by the aforementioned General Formula(1), if m is 0, X is a bivalent bond group or single bond and l+n is 2in the formula, then the polynuclear polyphenol is a bisphenol expressedby General Formula (3) specified below, and wherein similarly thepolynuclear poly(formylphenol) expressed by the aforementioned GeneralFormula (2) is a bis(formylphenol) expressed by General Formula (4)specified below:

wherein all Rs may be the same or different and respectively represent ahydrogen atom or an aliphatic hydrocarbon group that may have anaromatic hydrocarbon group, hydroxyl group, or aliphatic hydrocarbongroup that may have an ether group, where n indicates an integer of 0 or1 to 3; both R₁s may be the same or different and respectively representa hydrocarbon group, hydrocarbon group containing oxygen atom,halogenated hydrocarbon group, hydroxyl group or halogen group. ; Xindicates a bivalent bond group or single bond;

wherein R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3).
 3. The method forproducing a polynuclear poly(formylphenol) according to claim 2,characterized in that a bis(hydroxymethylphenol) expressed by GeneralFormula (6), being a bisphenol expressed by the aforementioned GeneralFormula (3) where R is a hydrogen atom, is obtained by causing abisphenol expressed by General Formula (5) to react with formaldehyde inthe presence of an alkali catalyst:

wherein R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3), and at least one of theo-position and p-position of the hydroxyl group is not substituted;

wherein R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3), and the substitutionposition of the hydroxy methyl group corresponds to the o-position orp-position relative to the hydroxyl group.
 4. The method for producing apolynuclear poly(formylphenol) according to claim 2, characterized inthat a bis(alkoxymethylphenol), being a bisphenol expressed by theaforementioned General Formula (3) where R is an aliphatic hydrocarbongroup that may have an aromatic hydrocarbon group, hydroxyl group oraliphatic hydrocarbon group that may have an ether group, is obtained bycausing a bisphenol expressed by General Formula (5) to react withformaldehyde in the presence of an alkali catalyst and then causing theobtained bis(hydroxymethylphenol) expressed by General Formula (6) tofurther react with an alcohol expressed by the General Formula (7)specified below in the presence of an acid catalyst:

wherein R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3), and at least one of theo-position and p-position of the hydroxyl group is not substituted;

wherein R₁, n and X indicate the same things represented by thecorresponding symbols in General Formula (3), and the substitutionposition of the hydroxy methyl group corresponds to the o-position orp-position relative to the hydroxyl group;R—OH  General Formula (7) wherein R represents an aliphatic hydrocarbongroup that may have an aromatic hydrocarbon group, hydroxyl group oraliphatic hydrocarbon group that may have an ether group.
 5. The methodfor producing a polynuclear poly(formylphenol) according to claim 1,wherein, with respect to a polynuclear polyphenol expressed by theaforementioned General Formula (1), the polynuclear polyphenol where min the formula indicates an integer of 0, 1 or 2, but where if m is 0,then X is a trivalent to hexavalent bond group and l+n is 3 to 6, is apolynuclear polyphenol expressed by General Formula (8) specified below,and wherein similarly the polynuclear (formylphenol) expressed by theaforementioned General Formula (2) is a polynuclear poly(formylphenol)expressed by General Formula (9) specified below:

wherein all Rs may be the same or different and respectively represent ahydrogen atom or an aliphatic hydrocarbon group that may have anaromatic hydrocarbon group, hydroxyl group, or aliphatic hydrocarbongroup that may have an ether group, R₁, R₂ and R₃ may be the same ordifferent and respectively represent a hydrocarbon group, hydrocarbongroup containing oxygen atom, hydroxyl group, halogen group orhalogenated hydrocarbon group; a and c respectively indicate an integerof 0 or 1 to 3, while b indicates an integer of 0, 1 or 2; l and nrespectively indicate an integer of 1 to 3; m indicates an integer of 0,1 or 2; X indicates a bond group or single bond; and Y indicates abivalent alkylene group, If ; if m is 0, however, X is a trivalent tohexavalent bond group and l+n is 3 to 6;

wherein R₁, R₂, R₃, a, b, c, l, m, n, X and Y indicate the same thingsrepresented by the corresponding symbols in General Formula (8).
 6. Themethod for producing a polynuclear poly(formylphenol) according to claim5, characterized in that a polynuclear poly(hydroxymethylphenol)expressed by General Formula (11) specified below, being a polynuclearpolyphenol expressed by the aforementioned General Formula (8) where Ris a hydrogen atom, is obtained by causing a polynuclear polyphenolexpressed by General Formula (10) specified below to react withformaldehyde in the presence of an alkali catalyst:

wherein R₁, R₂, R₃, a, b, c, l, m, n, X and Y indicate the same thingsrepresented by the corresponding symbols in General Formula (1), and atleast one of the o-position and p-position of the hydroxyl group is notsubstituted; if m is 0, however, X is a trivalent to hexavalent bondgroup and l+n is 3 to 6;

wherein R₁, R₂, R₃, a, b, c, l, m, n, X and Y indicate the same thingsrepresented by the corresponding symbols in General Formula (1), and thesubstituted position of the hydroxy methyl group corresponds to theo-position or p-position relative to the hydroxyl group; if m is 0,however, X is a trivalent to hexavalent bond group and l+n is 3 to
 6. 7.The method for producing a polynuclear poly(formylphenol) according toclaim 5, characterized in that a polynuclear poly(alkoxymethylphenol),being a polynuclear polyphenol expressed by the aforementioned GeneralFormula (8) where R is an aliphatic hydrocarbon group that may have anaromatic hydrocarbon group, hydroxyl group or aliphatic hydrocarbongroup that may have an ether group, is obtained by causing a polynuclearpolyphenol expressed by General Formula (10) to react with formaldehydein the presence of an alkali catalyst and then causing the obtainedpolynuclear poly(hydroxymethylphenol) expressed by General Formula (11)to further react with an alcohol expressed by General Formula (12)specified below in the presence of an acid catalyst:

wherein R₁, R₂, R₃, a, b, c, l, m, n, X and Y indicate the same thingsrepresented by the corresponding symbols in General Formula (1), and atleast one of the o-position and p-position of the hydroxyl group is notsubstituted; if m is 0, however, X is a trivalent to hexavalent bondgroup and l+n is 3 to 6;

wherein R₁, R₂, R₃, a, b, c, l, m, n, X and Y indicate the same thingsrepresented by the corresponding symbols in General Formula (1), and thesubstituted position of the hydroxy methyl group corresponds to theo-position or p-position relative to the hydroxyl group. If m is 0,however, X is a trivalent to hexavalent bond group and l+n is 3 to 6;R—OH  General Formula (12) wherein R represents an aliphatic hydrocarbongroup that may have an aromatic hydrocarbon group, hydroxyl group oraliphatic hydrocarbon group that may have an ether group.